Tobacco substitute smoking material

ABSTRACT

Tobacco substitute based smoking mixture with added protein and phenyl acetic acid and/or 2-phenyl ethanol. The protein serves to reduce or eliminate the intensity of the off-odours and offflavours of the smoke from the substitute smoking material and imparts a tobacco-like flavour and after-taste to the smoke. The phenyl acetic acid and/or 2-phenyl ethanol serve to mask any off-notes arising from the protein. The tobacco substitute base utilized is preferably a carbohydrate material which has been subjected to a catalytic degradation at a temperature of at least 200* C. to a point at which it constitutes about 90 percent or less of the dry weight of the original carbohydrate.

United States Patent 1191 Anderson June 25, 1974 [54] TOBACCO SUBSTITUTESMOKING 2,809,904 10/1957 Koree.. .......131/2 MATERIAL 3,461,879 8/1969Kirkland ..l31/2 [75] Inventor: Robert Craig Anderson, West Kilbride,Scotland [73] Assignee: Imperial Chemical Industries Limited, London,England 22 Filed: Mar. 18, 1971 21 App]. No.: 125,810

[30] Foreign Application Priority Data Mar. 23, 1970 Great Britain13865/70 [52] US. Cl 131/2, 131/17, 131/144 [51] Int. Cl. A24b 15/00,A24b 15/04 [58] Field of Search 131/2, 17, 140-144 [56] References CitedUNITED STATES PATENTS 1,842,266 l/l932 Hicks 131/144 1,954,109 4/1934Whitaker 131/144 2,171,986 9/1939 Poetschke 131/9 X 2,930,720 3/1960Finberg 131/17 R 3,006,347 10/1961 Keaton 131/17 3,009,836 11/1961Samfield et a1, 131/17 AC 3,145,717 8/1964 Osborne et a1 131/140 C3,404,691 10/1968 3,478 015 11/1969 3,608,560 9/1971 Briskin et a1 ..13U2 2,576,021 11/1951 1( oree. 131/2 3,280,823 10/1966 Bavley et a1131/262 A 2,766,148 10/1956 Rowland ..l31/17 R 3,545,448 12/1970 Mormanet a1 ..131/2 3,106,210 10/1964 Reynoldsetal ..13l/17R 3,025,860 3/1962Grossteinbeck et a1 131/140 C FOREIGN PATENTS OR APPLICATIONS 10/1962Great Britain 131/17 OTHER REFERENCES N. Irving Sax (text) DangerousProperties of Industrial Materials Third Edition (1968) Published by theReinhold Book Corporation, New York, pp. 1006 and 1008.

Primary Examiner-Melvin D. Rein Attorney, Agent, or Firm-Cushman, Darby& Cushman [57 ABSTRACT ,1 1 Tobacco substitute based smoking mixturewith added protein and phenyl acetic acid and/or 2-pheny1 ethanol. Theprotein serves to reduce or eliminate the intensity of the off-odoursand off-flavours of the smoke from the substitute smoking material andimparts atobacco-like flavour and after-taste to thesmoke.

5 Claims, No Drawings TOBACCO SUBSTITUTE SMOKING MATERIAL This inventionrelates to a smoking mixture suitable for incorporation in cigars,cigarettes and smoking pipes, in total or partial replacement of thetobacco constituent of the mixtures normally used.

Smoking mixtures normally consist mainly of, or contain a highproportion of natural tobacco and the opinion is now widely held thatthe smoking of tobacco, especially in cigarette fonn, increases theincidence of lung cancer and bronchitic ailments. The replacement oftobacco in smoking mixtures by cellulose and other smoke-producingmaterials has been proposed but such proposed mixtures have not beenacceptable to smokers because the smoke flavour was excessivelydifferent from that of tobacco smoke.

It is an object of this invention to provide a smoking mixturecomprising an organic combustible material as smoke producing fuel whichwill give asmoke resembling tobacco smoke in flavour.

In copending U.S. application Ser. No. 125,812, filed on even dateherewith, we described how this object can be fulfilled to'some extentby the inclusion of protein in the smoking mixture. The protein servesto reduce or eliminate the intensity of the off-odours and off-flavoursof the smoke from the substitute smoking material and also imparts atobacco-like flavour and after-taste to the smoke. Such an improvedsmoking mixture containing protein to mask the unpleasant character ofthe smoke produced therefrom is not, however, entirely satisfactorysince the protein itself can give rise to off-notes or odours.

It is a further object, therefore, of this invention to improve on theprotein-containing smoking mixtures of our aforesaid application Ser.No. 125,812 by including an ingredient which masks the protein off-notesof the smoke from said mixtures.

According to the present invention there is provided a smoking mixturecomprising an organic combustible material as smoke producing fuel,protein and phenyl acetic acid and/or 2-phenyl ethanol.

The amount of protein to smoke-producing fuel is in the range 1:1 to1:60, preferably 1:8 to 1:30.

The smoking mixture of the invention may comprise a minimum of 25percent by weight of the aforesaid smoke-producing fuel up to 7 percentby weight of protein, up to 0.02 percent of phenyl acetic acid and/or0.2 percent of Z-phenyl ethanol.

The organic combustible material may be a smokeproducing carbohydrate.

The smoke-producing carbohydrate may advantageously comprisea-cellulose, cellulose derivatives, sugars, starch, alginate, pectin ornatural gum.

The organic combustible material may be a modified carbohydrate.

The modified carbohydrate may advantageously be prepared as disclosed inour U.S. Pat. No. 1,113,979 by subjecting it to a catalysed degradationprocess at a temperature of 100-250C until the weight of the degradedmaterial is less than 90 percent of the dry weight of the originalcarbohydrate.

Preferred degradation catalysts include sulphuric acid, sulphamic acidand ammonium sulphamate.

A preferred modified carbohydrate is thermally degraded cellulose.

The modified carbohydrate may also be oxidised cellulose. The organiccombustible material may be a solid condensate as described inco-pending U.S. application Ser. No. 31014, filed Apr. 22, 1970, and nowU.S. Pat. No. 3,705,589 of Dec. 12, 1972, and produced by acid or basedcatalysed condensation of a compound of the formula RCO CH CH COR (I)(or a precursor thereof), wherein R and R which may be the same ordifferent, each represents a hydrogen atom, or an alkyl, hydroxyalkyl orformyl group. Said condensate may be prepared from succinaldehyde,acetonyl acetone or a precursor of (I) which is a compound containing afuran ring structure.

The protein should preferably be pure and it is desirable, but notessential, that any residual fat should be removed from the protein, forexample, by extraction with an organic solvent. Especially valuableproteins include animal protein, for example, albumin, casein, gelatine,peptone, haemoglobin or wool protein and vegetable proteins, forexample, protein from maize (zein) wheat (glutin and gliadin), soyabeanorgroundnut. Protein acid hydrolysates and protein enzyme hydrolysates,particularly casein a-cid hydrolysate and casein enzyme hydrolysate, arealso suitable.

The smoking mixtures of the invention will, in addition to protein andthe smoke-producing constituent and phenyl acetic acid and/or 2-phenylethanol contain other ingredients such as are normally used in smokingmixtures to impart desired physical properties and burningcharacteristics. For example, the mixtures may comprise glow-controllingcatalysts, materials to improve ash coherence and colour, nicotine,flavourants, medicaments and humectants or film-forming binding agents.The mixtures may also contain tobacco as part of the smoke-producingmaterial. Such added tobacco could be in the form of comminuted tobaccoor tobacco shred.

More particularly, additional compounds may comprise:

1. Fillers e.g., calcium carbonate, magnesium carbonate.

2. Humectants e.g., glycerol, ethylene glycol, polyethylene glycol.

3. Film-forming agents e.g., methyl cellulose, sodium carboxymethylcellulose, pec'tins, gums.

4. Glow-controlling catalysts e.g., potassium citrate, calciumcarbonate, magnesium carbonate.

5. Ash cohesion agents e.g., citric acid, sodium hydrogen phosphate,tobacco extracts.

6. Solanesol, other similar unconjugated polyisoprenoids and derivativesthereof (e.g., esters, acids and hydroxyl derivatives), may be added toobtain a sweetish aroma from the burning mixture and to give a pleasantafter-note in the mouth of the smoker.

The smoking mixture containing modified carbohydrate or aldolcondensation product may additionally contain as a minor component oneor more carbohydrate materials such as cellulose fibre, starch or sugar,to improve flavour and physical properties.

The smoking mixture is preferably prepared in a form simulating tobacco.Thus it is preferred to form the mixed ingredients into a sheet and cutor shred into the physical form required. If the smoke-producingmaterial used is already sheeted, the smoking mixture may be prepared bymerely treating the sheet with the remaining ingredients. in the usualcase, where the smoke-producing material is in divided form, theingredients may be admixed and subsequently sheeted. To facilitatesheeting, it is advantageous to incorporate a solution of a bindingagent, for example, water-soluble cellulose ether, polyvinyl alcohol ora water-soluble gum, in the mixture.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight. I

The Examples illustrate that the desired effect can be achieved byadding phenyl acetic acid or Z-phenyl ethanol to the smoking mixture orby adding both compounds together to the mixture. The Examples alsoillustrate that the addition of these compounds has little positiveinfluence on the flavour of tobacco substitute material if protein isabsent. The effect is thus synergistic between the substitute compoundsand protein. In each of the Examples the flavour and after-taste of theproduct were assessed by a panel of smokers. Furthermore, in eachExample, those ingredients which are not soluble, are to be consideredas being finely divided.

EXAMPLE 1 2.8 parts glycerol, 0.8 part citric acid and 1.0 partpotassium citrate were dissolved in 20 parts distilled water and theresultant solution added to a stirred solution of 2 parts of sodiumcarboxymethyl cellulose in 80 parts hot distilled water. 1.27 partscasein (fat-free) 2 parts calcium carbonate and 10.13 parts of amaterial made by heating a-cellulose impregnated with 0.51 part ofammonium sulphamate for 4 hours at 200C, were added to the abovesolution and the slurry stirred until homogeneous (approximately 1hour).

The slurry was cast on glass plates to form a film 0.006 in. thick whichwas shredded. The shred was sprayed with an ether solution containing0.004 part of phenyl acetic acid, the ether removed by evaporation andthe shred made into cigarettes. When smoked, the cigarettes had atobacco-like flavour and after-taste. This effect was superior to thatfrom a similar cigarette without phenyl acetic acid added.

In a similar composition in which the casein was re placed by ammoniumsulphate, thus eliminating any protein flavour effect yet keeping thesmoke pH the same as before, phenyl acetic acid produced a smoke inwhich no tobacco flavour was evident.

EXAMPLE 2 2.8 parts of glycerol, 0.8 part citric acid and part potassiumcitrate were dissolved in 20 parts distilled water and the resultantsolution added to a stirred solution of 2 parts of sodium carboxymethylcellulose in 80 parts hot distilled water. 0.88 part casein (fat-free),2 parts of calcium carbonate and 10.52 parts of a material made byheating a-cellulose impregnated with 0.51 part of ammonium sulphamatefor 4 hours at 200C, were added to the above solution and the slurrystirred until homogenous (approximately 1 hour).

The slurry was cast on glass plates to form a film 0.006 in. thick whichwas shredded. The shred was sprayed with an ether solution containing0.004 part of phenyl acetic acid, the ether removed by evaporation andthe shred made into cigarettes. When smoked, the

cigarettes had a tobacco-like flavour and after-taste. The same resultwas obtained when the 0.004 part of phenyl acetic acid was incorporatedinto the slurry mix instead of spraying on to the shred.

This Example illustrates the desired effect with a lower proportion ofcasein included in the smoking mixture.

EXAMPLE 3 2.8 parts of glycerol, 0.8 part citric acid and 1.0 partpotassium citrate were dissolved in 20 parts distilled water and theresultant solution added to a stirred solution of 2 parts of sodiumcarboxymethyl cellulose in parts hot distilled water. 0.88 part casein(fat-free), 2 parts of calcium carbonate and 10.52 parts of a materialmade by heating a-cellulose impregnated with 0.51 part of ammoniumsulphamate for 4 hours at 200C, were added to the above solution and theslurry stirred until homogeneous (approximately 1 hour).

The slurry was cast on glass plates to form a film 0.006 in. thick whichwas shredded. The shred was sprayed with an ether solution containing0.002 part of phenyl acetic acid, theether removed by evaporation andthe shred made into cigarettes.

When smoked, the cigarettes had a tobacco-like flavour and after-taste.

This Example illustrates the desired effect being obtained with a lowerproportion of phenyl acetic acid in the smoking mixture.

EXAMPLE 4 2.8 parts glycerol, 0.8 part citric acid and 1.0 partpotassium citrate were dissolved in 20 parts distilled water and theresultant solution added to a stirred solution of 2 parts of sodiumcarboxymethyl cellulose in 80 parts hot distilled water. 0.88 partcasein (fat-free), 2 parts of calcium carbonate and 10.52 parts of amaterial made by heating a-cellulose impregnated with 0.51 part ofammonium sulphamate for 4 hours at 200C, were added to the abovesolution and the slurry stirred until homogeneous (approximately 1hour).

The slurry was cast on glass plates to form a film 0.006 in. thick whichwas shredded. The shred was sprayed with an ether solution containing0.02 part 2- phenyl ethanol, the ether removed by evaporation and theshred made into cigarettes.

When smoked, the cigarettes had protein off-notes and rank notes reducedwith tobacco-like after-taste and a hint of tobacco flavour present.

EXAMPLE 5 2.8 parts glycerol, 0.8 part citric acid and 1.0 partpotassium citrate were dissolved in 20 parts distilled water and theresultant solution added to a stirred solution of 2 parts of sodiumcarboxymethyl cellulose in 80 parts hot distilled water. 0.88 partcasein (fat-free), 2 parts of calcium carbonate and 10.52 parts ofmaterial made by heating oz-cellulose impregnated with 0.51 part ofammonium sulphamate for 4 hours at 200C, were added to the abovesolution and the slurry stirred until homogeneous (approximately 1hour).

The slurry was cast on glass plates to form a film 0.006 in. thick whichwas shredded. The shred was sprayed with an ether solution containing0.008 part of 2-phenyl ethanol, the ether removed by evaporation and theshred made into cigarettes.

When smoked, the cigarettes had a faint tobacco-like flavour andtobacco-like after-taste. Rank protein offnotes were considerablyreduced compared to the same composition without Z-phenyl ethanol.

EXAMPLE 6 2.8 parts glycerol, 0.8 part citric acid and 1.0 partpotassium citrate were dissolved in parts distilled water and theresultant solution added to a stirred solution of 2 parts of sodiumcarboxymethyl cellulose in 80 parts hot distilled water. 0.88 partcasein (fat-free), 2 parts of calcium carbonate and 10.52 parts of amaterial made by heating a-cellulose impregnated with 0.51 part ofammonium sulphamate for 4 hours at 200C, were added to the abovesolution and the slurry stirred until homogeneous (approximately 1hour).

The slurry was cast on glass plates to form a film 0.006 in. thick whichwas shredded. The shred was sprayed with an ether solution containing0.002 part phenyl acetic acid and 0.02 part 2-phenyl ethanol, the etherremoved by evaporation and the shred made into cigarettes.

When smoked, the cigarettes had a sweet tobaccolike flavour andtobacco-like after-taste. The flavour was superior to the similarcomposition without 2- phenyl ethanol (Example 4) and protein off-odourswere not so readily detected.

EXAMPLE 7 2.8 parts glycerol, 0.8 part citric acid and 1.0 partpotassium citrate were dissolved in 20 parts distilled water and theresultant solution added to a stirred solution of 2 parts of sodiumcarboxymethyl cellulose in 80 parts hot distilled water. 0.56 partscasein (fat-free), 2 parts of calcium carbonate and 10.84 parts of amaterial made by heating a-cellulose impregnated with 0.51 part ofammonium sulphamate for 4 hours at 200C, were added to the abovesolution and the slurry stirred until homogeneous (approximately 1hour).

The slurry was cast on glass plates to form a film 0.006 in. thick whichwas shredded. The shred was sprayed with an ether solution containing0.001 part of phenyl acetic acid and 0.01 part 2-phenyl ethanol, theeither removed by evaporation and the shred made into cigarettes.

When smoked, the cigarettes had weak tobacco-like flavour andtobacco-like after-taste.

EXAMPLE 8 1.34 parts of glycerol and 0.78 part of potassium citratedissolved in 4 parts distilled water were mixed with 1.92 parts ofsodium carboxymethyl cellulose dissolved in 96 parts hot distilledwater. 6.72 parts of magnesium carbonate (magnesite), 3.86 parts ofcalcium carbonate, 0.2 part of protein casein (extracted for 48 hourswith petroleum ether at 30C) and 5.18 parts of a material made byheating a-cellulose with ammonium sulphamate for up to 4 hours at 200C,were added to the above mixture and the whole stirred until homogeneous(about 1 hour).

The slurry was cast on glass plates to give a film 0.006 in. thick whichwas dried, removed from the plates, cut and shredded. This shred wassprayed with a solution of 0.0002 part of phenyl acetic acid and 0.0004part of Z-phenyl ethanol in 50 parts of ether and the solvent allowed toevaporate.

When the treated shred was made into cigarettes in a 50:50 blend withflue-cured tobacco shred and smoked in comparison with a similar blendwith the two additives missing, there was a marked preference for theformer cigarette because of the presence of a fuller flue-cured tobaccoflavour.

Assimilar result was obtained in similar exercises using either :30 or:15 shred/shred blends of the modified cellulose mixture and flue-curedtobacco respectively.

EXAMPLE 9 1.34 parts of glycerol and 0.78 part of potassium citratedissolved in 4 parts distilled water were mixed with 1.92 parts ofsodium carboxymethyl cellulose dissolved in 96 parts hot distilledwater. 6.72 parts of magnesium carbonate (magnesite), 3.86 parts ofcalcium carbonate, 0.2 part of protein casein (extracted for 48 hourswith petroleum ether at 30C) and 5.18 parts of a material made byheating a-cellulose with ammonium sulphamate for up to 4 hours at 200C,were added to the above mixture and the whole stirred until homogeneous(about 1 hour).

The slurry was cast on glass plates to give a film 0.006 in. thick whichwas dried, removed from the plates, cut and shredded. This shred wassprayed with a solution of 0.0002 part of phenyl acetic acid, 0.0004part 2- phenyl ethanol and 0.01 part of carotene (as a mixture ofisomers 85 percent 13-, 15 percent a-carotene) in 35 parts of carbontetrachloride and the solvent allowed to evaporate.

When the threated shred was made up into cigarettes in a 50:50 blendwith flue-cured tobacco shred and smoked in comparison with a similarblend with phenyl acetic acid and 2-phenyl ethanol missing, there was amarked preformance for the former cigarette because of the presence of afuller flue-cured tobacco flavour.

A similar result was obtained in similar exercises using a 70:30shred/shred blend of modified cellulose mixture and flue-cured tobaccorespectively.

EXAMPLE 1.34 parts of glycerol and 0.78 part of potassium citratedissolved in 4 parts of distilled water were mixed with 1.92 parts ofsodium carboxymethyl cellulose dissolved in 96 parts hot distilledwater. 6.72 parts of magnesium carbonate (magnesite), 3.86 parts ofcalcium carbonate, 0.38 part of the protein casein (extracted for 48hours with petroleum etherat 30C) and 5.0 parts of rice starch wereadded to the above mixture and the whole stirred until homogeneous(about .1 hour).

The slurry was cast on glass plates to give a film 0.006 in. thick whichwas dried, removed from the plates, cut and shredded. The shred wassprayed with a solution of 0.0002 part of phenyl acetic acid and 0.002part of 2- phenyl ethanol in 50 parts ether and the solvent allowed toevaporate. When the treated shred was made into cigarettes and smoked incomparison with a similar cigarette not containing the two sprayed-onadditives, there was a marked preference for the cigarette with theadditives because of its improved tobacco character.

EXAMPLE 11 1.34 parts of glycerol and 0.78 part of potassium citratedissolved in 4 parts of distilled water were mixed with 1.92 parts ofsodium carboxymethyl cellulose dissolved in 96 parts hot distilledwater. 6.72 parts of magnesium carbonate (magnesite), 3.86 parts ofcalcium carbonate, 0.38 part of the protein casein (extracted for 48hours with petroleum ether at 30C) and 5.0 parts of a-cellulose wereadded to the above mixture and the whole stirred until homogeneous(about 1 hour).

The slurry was cast on glass plates to give a film 0.006 in. thick whichwas dried, removed from the plates, cut and shredded. The shred wassprayed with a solution of 0.0002 part of phenyl acetic acid and 0.002part of 2- phenyl ethanol in 50 parts ether and the solvent allowed toevaporate. When the treated shred was made into cigarettes and smoked incomparison with a similar cigarette not containing the two sprayed-onadditives, there was a marked preference for the cigarette with theadditives because of its improved tobacco character.

EXAMPLE 12 1.8 parts of glycerol dissolved in 4 parts of distilled waterwere mixed with 2.4 parts sodium carboxymethyl cellulose dissolved in 96parts distilled water. 5.98 parts of magnesium carbonate (magnesite),3.44 parts of calcium carbonate, 0.3 parts of zein protein, 1 partbentonite and 5.08 parts of a material made by heating a-cellulose withammonium sulphamate were added to the above mixture and the wholestirred until homogeneous (about 1 hour).

The slurry was cast on glass plates and dried to give a film 0.006 in.thick. The film was removed, shredded and the shred was sprayed with asolution of 0.001 part of phenyl acetic acid and 0.002 part of 2-phenylethanol, in 50 parts ether and the solvent allowed to evaporate. Whenthe treated shred was made into cigarettes and smoked, in comparisonwith a similar cigarette not containing the two sprayed-on additives,there was a marked preference for the cigarettes with the additivebecause of improved tobacco character.

EXAMPLE 13 1.8 parts of glycerol dissolved in 4 parts of distilled waterwere mixed with 2.4 parts sodium carboxymethyl cellulose dissolved in 96parts distilled water. 5.98 parts of magnesium carbonate (magnesite 3.44parts of calcium carbonate, 2.69 parts of casein protein and 1 part ofbentonite and 2.69 parts of a material made by heating a-cellulose withammonium sulphamate were added to the above mixture and the wholestirred until homogeneous (about 1 hour).

The slurry was cast on glass plates and dried to give a film 0.006 in.thick. The film was removed shredded and the shred was sprayed with asolution of 0.001 part of phenyl acetic acid and 0.002 part of 2-phenylethanol in 50 parts ether and the solvent allowed to evaporate. When thetreated shred was made into cigarettes and smoked in comparison with asimilar cigarette not containing the two sprayed'on additives, there wasa marked preference for the cigarettes with the additive because ofimproved tobacco character.

EXAMPLE 14 1.8 parts of glycerol dissolved in 4 parts of distilled waterwere mixed with 2.4 parts sodium carboxymethyl cellulose dissolved in 96parts distilled water. 5.98 parts of magnesium carbonate (magnesite),3.44 parts of calcium carbonate, 0.088 parts of casein protein, 1 partbentonite and 5.21 parts of a material made by heating oz-cellulose withammonium sulphamate were added to the above mixture and the wholestirred until homogeneous (about 1 hour).

The slurry was cast on glass plates and dried to give a film 0.006 in.thick. The film was removed, shredded and the shred was sprayed with asolution of 0.001 part of phenyl acetic acid and 0.002 part of 2-phenylethanol in 50 part ether and the solvent allowed to evaporate. When thetreated shred was made into cigarettes and smoked in comparison with asimilar cigarette not containing the two sprayed-on additives, there wasa marked preference for the cigarettes with the additive because ofimproved tobacco character.

EXAMPLE 15 1.8 parts of glycerol dissolved in 4 parts of distilled waterwere mixed with 2.4 parts sodium carboxymethyl cellulose dissolved in 96parts distilled water. 5 .08 parts of magnesium carbonate (magnesite),2.92 parts of calcium carbonate, 1.4 parts of casein protein and 1 partbentonite and 5.38 parts of a material made by heating cit-cellulosewith ammonium sulphamate were added to the above mixture and the wholestirred until homogeneous (about 1 hour).

The slurry was cast on glass plates and dried to give a film 0.006 in.thick. The film was removed, shredded and the shred was sprayed with asolution of 0.004 part of phenyl acetic acid and 0.04 part of 2-phenylethanol in 50 parts ether and the solvent allowed to evaporate. When thetreated shred was made into cigarettes and smoked in comparison with asimilar cigarette not containing the two sprayed-on additives, there wasa marked preference for the cigarettes with the additive because ofimproved tobacco character.

EXAMPLE 16 1.8 parts of glycerol dissolved in 4 parts of distilled waterwere mixed with 2.4 parts sodium carboxymethyl cellulose dissolved in 96parts distilled water. 5.98 parts of magnesium carbonate (magnesite),3.44 parts of calcium carbonate, 0.3 parts casein and 1 part bentoniteand 5.08 parts of a condensate of succinaldehyde (see US. Pat.application Ser. No. 31014) were added to the above mixture and thewhole stirred until homogeneous (about 1 hour).

The slurry was cast on glass plates and dried to give a film 0.006 in.thick. The film was removed, shredded and the shred was sprayed with asolution of 0.001 part of phenyl acetic acid and 0.002 part of 2-phenylethanol in 50 parts ether and the solvent allowed to evaporate. When thetreated shred was made into cigarettes and smoked in comparison with asimilar cigarette not containing the two sprayed-on additives, there wasa marked preference for the cigarettes with the additive because ofimproved tobacco character.

EXAMPLE 17 1.8 parts of plycerol dissolved in 4 parts of distilled waterwere mixed with 2.4 parts sodium carboxymethyl cellulose dissolved in 96parts distilled water, 5 .98 parts of magnesium carbonate (magnesite), 3.44 parts of calcium carbonate, 0.3 parts of soya protein, 1 partbentonite and 5.08 parts of a material made by heating a-cellulose withammonium sulphamate were added to the above mixture and the wholestirred until homogeneous (about 1 hour).

The slurry was cast on glass plates and dried to give a film 0.006 in.thick. The film was removed, shredded and the shred was sprayed with asolution of 0001 part of phenyl acetic acid and 0002 part of 2-phenylethanol in 50 parts ether and the solvent allowed to evaporate. When thetreated shred was made into cigarettes and smoked in comparison with asimilar cigarette not containing the two sprayed-on additives, there wasa marked preference for the cigarettes with the additive because ofimproved tobacco character.

' EXAMPLE 18 0.34 parts glycerol were dissolved in 4 parts distilledwater and mixed with 6.6 parts sodium carboxy-methyl cellulose dissolvedin 96 parts water. 6.2 parts dolomite (Dolodust), 5.6 parts diatomaceousearth (celite), 0.22 part charcoal, 0.34 part octanol and 0.4 partcasein protein were added to the above mixture and the whole stirreduntil homogeneous (about 1 hour).

The slurry was cast on glass plates and dried to give a film 0.006 in.thick. The film was removed, shredded and sprayed with a solution of0.0004 parts phenyl acitic-acid and 0.0008 parts 2-phenyl ethanol in 50parts ether and the solvent allowed to evaporate. When the treated shredwas made into cigarettes and smoked in comparison with similarcigarettes not containing the two sprayed on additives there was amarked preference for the cigarettes with the two sprayed on additivesbecause of improved taste and after-taste which had a cigar/pipe tobacconature.

What I claim is:

l. A smoking mixture comprising a thermally degraded carbohydratetobacco substitute as the essential smoke-producing fuel, a proteinselected from the group consisting of casein, groundnut protein,soyabean protein, zein, albumin or gliadin, the amount of protein tosmoke-producing fuel being in the range 1:8 to 1:60 and a sufiicientamount of a member of the group consisting of phenyl acetic acid and2-phenyl ethanol to mask any off-notes from the protein, said thermallydegraded carbohydrate being obtained by subjecting a carbohydratematerial to a catalysed degradation process at a temperature of at least100 C. until the weight of the degraded material is approxi matelypercent or less of the dry weight of the original carbohydrate.

2. A smoking mixture as claimed in claim 1 wherein the amount of proteinto smoke-producing fuel is in the range 1:8 to 1:30.

3. A smoking mixture as claimed in claim 1 consisting essentially of thesmoke-producing fuel, up to 7 percent by weight of protein, up to 0.02percent of phenyl acetic acid and/or 0.2 percent of Z-phenyl ethanol.

4. A smoking mixture as claimed in claim 1 wherein the modifiedcarbohydrate comprises thermally degraded cellulose.

5. A smoking mixture as claimed in claim 1 wherein the protein is pureprotein free of residual fat.

2. A smoking mixture as claimed in claim 1 wherein the amount of pRoteinto smoke-producing fuel is in the range 1:8 to 1:30.
 3. A smokingmixture as claimed in claim 1 consisting essentially of thesmoke-producing fuel, up to 7 percent by weight of protein, up to 0.02percent of phenyl acetic acid and/or 0.2 percent of 2-phenyl ethanol. 4.A smoking mixture as claimed in claim 1 wherein the modifiedcarbohydrate comprises thermally degraded cellulose.
 5. A smokingmixture as claimed in claim 1 wherein the protein is pure protein freeof residual fat.